CN112920687B - Single-component flake type epoxy zinc-rich anti-corrosive primer and preparation method thereof - Google Patents
Single-component flake type epoxy zinc-rich anti-corrosive primer and preparation method thereof Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F9/00—Compounds to be used as driers (siccatives)
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention discloses a single-component flake-type epoxy zinc-rich anti-rust primer and a preparation method thereof, belongs to the field of industrial anti-corrosion coatings, and solves the problems of poor flexibility of a paint film, serious precipitation of zinc powder and poor salt spray resistance of the existing anti-corrosion coating. The anti-rust primer of the invention comprises: linseed oil modified epoxy resin, a dispersing agent, bentonite, fumed silica, flaky zinc powder, glass flakes, nano nickel-titanium alloy, superfine ferrophosphorus powder, a drier cobalt isooctanoate, an adhesion promoter, xylene and butyl acetate. The preparation method comprises the following steps: sequentially adding linseed oil modified epoxy resin, a dispersing agent, bentonite, fumed silica, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder, and uniformly stirring; increasing the rotating speed and dispersing at a high speed; adding drier cobalt iso-octoate, adhesion promoter, xylene and butyl acetate under stirring; and (6) filtering and packaging. The anti-rust primer disclosed by the invention is excellent in performance and convenient to prepare.
Description
Technical Field
The invention belongs to the field of industrial anticorrosive coatings, and particularly relates to a single-component flake type epoxy zinc-rich anti-rust primer and a preparation method thereof.
Background
The anticorrosion of the paint is usually finished by a primer, an intermediate paint and a finish paint or a coating system with the mutual cooperation of the primer and the finish paint, the function of the primer in the whole coating system is particularly important, and the commonly used primers are as follows: double-component epoxy zinc-rich primer, single-component epoxy anti-rust primer and hot galvanizing coating. The epoxy zinc-rich primer is widely applied, has excellent corrosion resistance, has the advantages of excellent adhesion and heat resistance, no influence on welding and the like, and is a main matched primer in heavy-duty anticorrosive coatings of steel structure bridges, ships, docks, plants, pipelines, iron towers and the like. The common epoxy zinc-rich primer can be divided into national standard zinc-rich primer, workshop primer, special container primer, flake zinc powder primer and other anticorrosive products, which can be used as antirust primer, but have differences in specific applicable environment, coating process and other aspects, and can be reasonably selected according to coating requirements and the difficulty degree of coating construction in the actual use process.
The two-component epoxy zinc-rich primer has good corrosion resistance and good adhesive force with a steel substrate, but the flexibility of a paint film is poor, a product is divided into two components, namely a main paint and a curing agent, the two components are required to be added strictly according to a proportion during construction and are uniformly mixed for use, the construction procedures are increased, the quality problem of the product is possibly caused by artificial uncontrollable factors during allocation, the product is required to be used up within a specified time, and in addition, the product is dried slowly or even cannot be dried when being constructed at the temperature of below 5 ℃; meanwhile, the adopted spherical zinc powder is generally more than 80 percent in use amount and has the defect of serious precipitation during storage.
The existing single-component epoxy anti-corrosive primer has the problems of poor salt spray resistance, slow drying, poor adhesion and the like, can be only used in the field of light corrosion resistance of steel structures, and is not suitable for popularization and application in the field of heavy corrosion resistance.
The hot-dip galvanizing has the advantages of good corrosion resistance and good coating adhesiveness, but has the defects of poor working environment, serious pollution and the like. The hot-dip galvanizing process is carried out at high temperature, strong irritant hydrogen chloride gas can be separated out when the solvent is dried and the workpieces to be galvanized are immersed into the bath, the zinc bath is kept at high temperature for a long time, zinc vapor is generated on the surface, and the whole working environment is thatThe atmosphere is severe, and a large amount of SO is discharged into the atmosphere during the production2、CO2CO and dust fumes, causing severe atmospheric pollution.
Disclosure of Invention
The invention aims to provide a single-component flake-type epoxy zinc-rich anti-corrosive primer, which is used for solving the problems of poor flexibility of a paint film, difficulty in operation, serious precipitation of zinc powder, poor salt spray resistance, slow drying, poor adhesion and serious environmental pollution of the existing anti-corrosive paint.
The invention also aims to provide a preparation method of the single-component flake-type epoxy zinc-rich anti-rust primer.
The technical scheme of the invention is as follows: a single-component flake-type epoxy zinc-rich anti-rust primer comprises the following components in parts by weight: 20-35 parts of linseed oil modified epoxy resin, 0.2-0.5 part of dispersant, 0.5-1 part of bentonite, 0.5-1 part of fumed silica, 55-70 parts of flaky zinc powder, 20-35 parts of glass flake, 5-10 parts of nano nickel-titanium alloy, 3-8 parts of superfine ferrophosphorus powder, 0.2-0.5 part of drier cobalt isooctanoate, 0.5-1 part of adhesion promoter, 1-5 parts of xylene and 0.5-2 parts of butyl acetate; wherein the fineness of the superfine ferrophosphorus powder is 1500-2000 meshes.
As a further improvement of the invention, the fineness of the superfine ferrophosphorus powder is 2000 meshes.
As a further improvement of the invention, the fineness of the glass flake is 325 meshes.
As a further improvement of the invention, the modification method of the linseed oil modified epoxy resin is a solvent method.
As a further improvement of the invention, the particle size of the nano nickel titanium alloy is 60 nm.
As a further improvement of the invention, Picker AT204 is selected as the dispersant. The chemical composition of the birk AT204 wetting dispersant is a carboxylate solution of an electrically neutral polyamine amide, which is a controlled flocculation type adjuvant that not only improves pigment and filler wetting and pigment and filler dispersion stability, but also gels organically modified bentonite, producing bentonite slurries with improved flowability, processability and storage stability. In the single-component flake-type epoxy zinc-rich anti-corrosive primer disclosed by the invention, the Pickering AT204 wetting dispersant generates thixotropy, so that pigment flooding, pigment floating and pigment precipitation are prevented, and sagging is reduced.
A preparation method of a single-component flake-type epoxy zinc-rich anti-rust primer comprises the following steps:
A. at the rotation speed of 300-plus-one 500 r/min, sequentially adding linseed oil modified epoxy resin, a dispersing agent, bentonite, fumed silica, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder into a clean stirring kettle, and uniformly stirring;
B. the rotating speed is increased to 1100-1200 rpm, the high-speed dispersion is carried out for 40-60min, the temperature of the paint paste in the stirring process is not more than 50 ℃ (when the temperature is higher than 50 ℃, the organic bentonite can be accelerated to promote the ring opening of the epoxy group to generate self-polymerization, so that the storage stability of the system is influenced, even the gelation phenomenon occurs), and the detection fineness is not more than 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate, an adhesion promoter, xylene and butyl acetate under stirring at the rotating speed of 800 revolutions per minute of 500-;
D. filtering with 60-80 mesh sieve, and packaging.
The single-component flake-type epoxy zinc-rich anti-rust primer takes linseed oil fatty acid modified E12 epoxy resin as a film forming material, improves the drying speed and flexibility of a paint film, and further promotes the surface drying of the paint film by adding the drier cobalt iso-octoate; adding flaky zinc powder and glass flakes in a certain proportion, compounding nano nickel-titanium alloy powder and superfine ferrophosphorus powder, arranging the introduced flaky zinc powder and the glass flakes in a flaky manner, and enabling the flakes to be in parallel lap joint and in surface contact with each other, so that the coating is compact and has long corrosion route, the zinc consumption and the coating thickness in unit area are greatly reduced, and the shielding performance and the corrosion resistance of the coating are greatly improved; meanwhile, the added nano nickel-titanium alloy has the particle size of 60nm, and due to the small size effect, the defects of the coating can be effectively filled, the porosity is reduced, the compactness is enhanced, and the corrosion resistance of the product is further improved; meanwhile, a drier cobalt iso-octoate is added to accelerate the oxidative polymerization drying of the paint film.
Compared with the prior art, the invention has the following advantages:
1) the E12 epoxy resin has a large molecular weight, the chemical resistance of the esterified product of the epoxy resin is high, and the linseed oil is drying oil and has the advantages of air drying property, quick drying, good adhesion with steel, good weather resistance and chemical resistance and the like. The method for modifying the epoxy resin by the linseed oil comprises a melting method and a solvent method, wherein the melting method is synthesized by modifying through physical mechanical stirring, the quality of a finished product is unstable, the solvent method is adopted in the invention, the resin synthesized by esterification by the method is not easy to generate a gelation phenomenon, lower viscosity can be obtained by controlling temperature and reaction time, the quality of the finished product is stable and controllable, and a finally formed coating film is quick to dry at low temperature or normal temperature, good in adhesive force, and excellent in chemical resistance and corrosion resistance. According to the invention, the linseed oil fatty acid modified epoxy resin E12 is adopted, so that the drying speed, flexibility, adhesive force and chemical resistance of the product are improved.
2) The novel drier cobalt iso-octoate solution is added, so that the paint film is accelerated to be oxidized, polymerized and dried, and the drying speed of the paint film is increased. When the cobalt iso-octoate drier is used alone, if the coating is too thick, the surface is dry, and the inside is not dry, so that wrinkling and cracking are generated.
3) The invention adds flaky zinc powder and glass flakes, and then matches with nano nickel-titanium alloy powder to form a super-strong composite anticorrosive material system with resin. The flaky zinc powder and the glass flakes form a flaky parallel lap joint to form a labyrinth structure after synergistic action, and the physical barrier property of the coating can be effectively improved, so that the salt spray resistance and corrosion resistance of the product are improved. In addition, the lamellar structure can divide the coating into a plurality of small areas, can effectively reduce the internal stress of the coating, consume the fracture energy and improve the flexibility, the impact resistance and the wear resistance of the coating. In the prepared product, the flaky zinc powder has better conductivity in a coating layer than spherical zinc powder, the utilization rate of the zinc powder is improved, the cathode protection effect is better, the using amount of the flaky zinc powder is only 1/2 of the spherical zinc powder required by a common zinc-rich primer, the anti-corrosion performance of the flaky zinc powder is better than that of the spherical zinc-rich paint, and the cost of the zinc-rich paint can be greatly reduced. The salt spray corrosion resistance of the coating taking the flaky zinc powder as the main raw material is obviously superior to that of electrogalvanizing and hot galvanizing, and the coating has small pollution and meets the requirement of environmental protection. Meanwhile, the added nano nickel-titanium alloy is a functional material with high strength, corrosion resistance, good dispersibility and no toxicity, the particle size is 60nm, and due to the small size effect, the defect of the coating prepared by the nano nickel-titanium alloy can be effectively filled, the porosity is reduced, the compactness is enhanced, and the corrosion resistance of the product is further improved. The flaky zinc powder, the glass flakes and the nano nickel-titanium alloy powder are matched for use, the cathode protection effect of the zinc powder and the super-strong shielding effect of a lamellar structure are utilized to enable a coating film to have excellent anti-corrosion performance, the flaky zinc powder has strong covering capacity, floating capacity, shielding capacity and metallic luster, the flaky zinc powder and the glass flakes are arranged in a flaky manner, the parallel lap joint between the flakes is realized, the contact mode is surface contact, the coating is compact, the corrosion route is long, the zinc consumption amount in a unit area and the coating thickness are greatly reduced, the shielding performance and the corrosion resistance of the coating are greatly improved, and the salt spray resistance can reach more than 6000. Meanwhile, the nano nickel-titanium alloy has small particle size, large specific surface area and high surface energy, can interact with resin polymers in the coating, can form hydrogen bonds among nano particles, forms a loose network structure in the coating, prevents the precipitation and agglomeration of pigments and fillers in the coating, avoids the sagging during construction, and achieves the rheological effect. The nano particles and the modified epoxy resin have strong interaction, so that the glass transition temperature is raised, and the nano particles after surface treatment actually play a role of a crosslinking point in a matrix, so that the surface of the nano particles is favorable for entanglement of modified epoxy resin chains to form physical crosslinking; on the other hand, the surface treating agent on the surface is bonded with the matrix to form good interface combination between the filling particles and the matrix, and the surface treating agent plays a role of a chemical crosslinking point. Therefore, with the addition of the nano particles, the crosslinking density is increased, so that the glass transition temperature is increased, and the performances of the coating such as strength, glass transition temperature, scratch resistance and the like are improved.
4) The single-component scale-type epoxy zinc-rich anti-rust primer disclosed by the invention is a single component, can obviously improve the production and construction efficiency, is convenient and simple to construct, can be constructed at the temperature of between 5 ℃ below zero and 10 ℃ below zero, is slightly limited by the environmental temperature, and has the advantages of being quick to dry, good in paint film flexibility, excellent in anti-corrosion performance and the like.
5) The invention adopts a high-speed stirring method for preparation, the method is simple, quick and easy to operate, and the synergistic effect among the raw materials is effectively utilized, thereby improving the corrosion resistance of the product, and reducing the energy loss and the environmental pollution.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
The specifications and the manufacturers of the raw materials used in the following examples are shown in Table 1.
Example 1, a one-component flake-type epoxy zinc-rich anti-rust primer comprises the following components:
preparing the following raw materials in parts by mass: 20 parts of linseed oil modified epoxy resin, 2040.5 parts of dispersant AT, 21 parts of bentonite SD-21, 9720.5 parts of fumed silica R, 70 parts of flaky zinc powder, 20 parts of glass flake, 5 parts of nano nickel-titanium alloy, 3 parts of superfine phosphorus iron powder, 0.2 part of drier cobalt isooctanoate, 5601 parts of adhesion promoter KH, 5 parts of xylene and 2 parts of butyl acetate;
the preparation method comprises the following steps:
A. AT the rotating speed of 300R/min, sequentially stirring linseed oil modified epoxy resin, a dispersant AT204, bentonite SD-2, fumed silica R972, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder in a clean stirring kettle uniformly;
B. the rotating speed is increased to 1200 r/min, the dispersion is carried out for 40min at a high speed, the temperature of the paint paste in the stirring process is not more than 50 ℃, and the detection fineness is not more than 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate, an adhesion promoter KH560, xylene and butyl acetate under stirring at the rotating speed of 800 r/min, stirring for 5min until the mixture is uniform, detecting that the viscosity meets 120-;
D. filtering with 60 mesh sieve, and packaging.
Example 2, a one-component flake-type epoxy zinc-rich anti-corrosive primer comprises the following components: preparing raw materials according to the following parts by mass: 25 parts of linseed oil modified epoxy resin, 2040.2 parts of dispersant AT, 20.5 parts of bentonite SD-20, 9720.8 parts of fumed silica, 65 parts of flaky zinc powder, 25 parts of glass flake, 6 parts of nano nickel-titanium alloy, 5 parts of superfine ferrophosphorus powder, 0.3 part of drier cobalt isooctanoate, 5600.8 parts of adhesion promoter KH, 4 parts of xylene and 1.5 parts of butyl acetate;
the preparation method comprises the following steps:
A. AT the rotating speed of 500R/min, sequentially stirring linseed oil modified epoxy resin, a dispersing agent AT204, bentonite SD-2, fumed silica R972 parts, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder in a clean stirring kettle uniformly;
B. the rotating speed is increased to 1100 r/min, high-speed dispersion is carried out for 50min, the temperature of the paint paste in stirring is not more than 50 ℃, and the detection fineness is not more than 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate, an adhesion promoter KH560, xylene and butyl acetate under stirring at the rotating speed of 700 r/min, stirring for 10min till uniformity, detecting that the viscosity meets 120-130KU and the specific gravity meets 2.8 +/-0.1 g/cm for nucleic acid production, and then qualified;
D. filtering with 80 mesh sieve, and packaging.
Example 3, a one-component flake-type epoxy zinc-rich anti-rust primer comprises the following components: preparing raw materials according to the following parts by mass: 30 parts of linseed oil modified epoxy resin, 30 parts of a dispersing agent AT 2040.2 parts, 20.5 parts of bentonite SD-20.5 parts, 9720.8 parts of fumed silica, 60 parts of flaky zinc powder, 30 parts of glass flakes, 8 parts of nano nickel-titanium alloy, 5 parts of superfine ferrophosphorus powder, 0.3 part of drier cobalt isooctanoate, 5600.6 parts of an adhesion promoter KH, 2 parts of xylene and 1 part of butyl acetate;
the preparation method comprises the following steps:
A. AT the rotating speed of 500R/min, sequentially stirring linseed oil modified epoxy resin, a dispersing agent AT204, bentonite SD-2, fumed silica R972 parts, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder in a clean stirring kettle uniformly;
B. the rotating speed is increased to 1100 r/min, high-speed dispersion is carried out for 50min, the temperature of the paint paste in stirring is not more than 50 ℃, and the detection fineness is not more than 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate, an adhesion promoter KH560, xylene and butyl acetate under stirring at the rotating speed of 600 r/min, stirring for 10min till uniformity, detecting that the viscosity meets 120-130KU and the specific gravity meets 2.7 +/-0.1 g/cm for nucleic acid production, and then qualified;
D. filtering with 80 mesh sieve, and packaging.
Example 4, a one-component flake-type epoxy zinc-rich anti-rust primer comprises the following components: preparing raw materials according to the following parts by mass: 35 parts of linseed oil modified epoxy resin, 2040.2 parts of dispersant AT, 20.5 parts of bentonite SD-20.5 parts, 9721 parts of fumed silica R, 55 parts of flaky zinc powder, 35 parts of glass flake, 10 parts of nano nickel-titanium alloy, 8 parts of superfine ferrophosphorus powder, 0.5 part of drier cobalt isooctanoate, 5600.5 parts of adhesion promoter KH, 1 part of xylene and 0.5 part of butyl acetate;
the preparation method comprises the following steps:
A. AT the rotating speed of 500R/min, sequentially stirring linseed oil modified epoxy resin, a dispersing agent AT204, bentonite SD-2, fumed silica R972 parts, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder in a clean stirring kettle uniformly;
B. the rotating speed is increased to 1200 r/min, the dispersion is carried out for 60min at a high speed, the temperature of the paint paste in the stirring process is not more than 50 ℃, and the detection fineness is not more than 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate, an adhesion promoter KH560, xylene and butyl acetate under stirring at a rotating speed of 500 r/min, stirring for 10min until the mixture is uniform, detecting that the viscosity meets 120-;
D. filtering with 80 mesh sieve, and packaging.
The single-component flake-type epoxy zinc-rich anti-corrosive primer prepared in the above embodiments is respectively prepared into a performance plate by spraying. According to the type requirements of chemical industry standard HG/T4342-2012 scale type zinc powder primer of the people's republic of China, the performance detection is shown in Table 2.
The product of the invention considers the common problems of the product in the field construction, and adds the performance detection of flexibility, storage property and low-temperature drying on the basis of the standard requirements, and the detection result is shown in the following table 2.
As can be seen from the table 2 and the subsequent table 2, the single-component flake type epoxy zinc-rich anti-corrosive primer prepared by the invention has the advantages of high drying speed, good flexibility, good adhesive force, no precipitation of zinc powder, good storage stability, excellent corrosion resistance and salt spray resistance of 6000 h.
Claims (3)
1. The single-component flake-type epoxy zinc-rich anti-rust primer is characterized by comprising the following components in parts by weight: 20-35 parts of linseed oil modified epoxy resin, 0.2-0.5 part of dispersant, 0.5-1 part of bentonite, 0.5-1 part of fumed silica, 55-70 parts of flaky zinc powder, 20-35 parts of glass flake, 5-10 parts of nano nickel-titanium alloy, 3-8 parts of superfine ferrophosphorus powder, 0.2-0.5 part of drier cobalt isooctanoate solution, 0.5-1 part of adhesion promoter, 1-5 parts of xylene and 0.5-2 parts of butyl acetate; wherein the fineness of the superfine ferrophosphorus powder is 1500-2000 meshes; the fineness of the glass flakes is 325 meshes; the particle size of the nano nickel-titanium alloy is 60 nm; the dispersant is Pick AT 204; the modification method of the linseed oil modified epoxy resin is a solvent method.
2. The one-component flake-type epoxy zinc-rich anti-rust primer as claimed in claim 1, which is characterized in that: the fineness of the superfine ferrophosphorus powder is 2000 meshes.
3. A method for preparing the one-component flake-type epoxy zinc-rich anti-rust primer according to claim 1 or 2, which is characterized by comprising the following steps:
A. at the rotation speed of 300-plus-one 500 r/min, sequentially adding linseed oil modified epoxy resin, a dispersing agent, bentonite, fumed silica, flaky zinc powder, glass flakes, nano nickel-titanium alloy and superfine ferrophosphorus powder into a clean stirring kettle, and uniformly stirring;
B. the rotating speed is increased to 1100-1200 rpm, the high-speed dispersion is carried out for 40-60min, the temperature of the paint paste in the stirring process is noted to be less than or equal to 50 ℃, and the detection fineness is less than or equal to 80 microns;
C. after the fineness is qualified, adding a drier cobalt iso-octoate solution, an adhesion promoter, xylene and butyl acetate under stirring at the rotating speed of 800 revolutions per minute of 500-;
D. filtering with 60-80 mesh fine basket, and packaging.
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| CN115181479A (en) * | 2022-08-17 | 2022-10-14 | 安徽省巢湖市通用锚链有限公司 | Maintenance coating for navigation mark ship |
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| CN112920687A (en) | 2021-06-08 |
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